[go: up one dir, main page]

WO2005086265A1 - Matériau de renfort pour membrane conductrice protonique, membrane conductrice protonique utilisant ledit matériau et une cellule électrochimique - Google Patents

Matériau de renfort pour membrane conductrice protonique, membrane conductrice protonique utilisant ledit matériau et une cellule électrochimique Download PDF

Info

Publication number
WO2005086265A1
WO2005086265A1 PCT/JP2005/003649 JP2005003649W WO2005086265A1 WO 2005086265 A1 WO2005086265 A1 WO 2005086265A1 JP 2005003649 W JP2005003649 W JP 2005003649W WO 2005086265 A1 WO2005086265 A1 WO 2005086265A1
Authority
WO
WIPO (PCT)
Prior art keywords
reinforcing material
proton conductive
binder
conductive membrane
nonwoven fabric
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2005/003649
Other languages
English (en)
Japanese (ja)
Inventor
Atsushi Asada
Juichi Ino
Noriaki Sato
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Sheet Glass Co Ltd
Original Assignee
Nippon Sheet Glass Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippon Sheet Glass Co Ltd filed Critical Nippon Sheet Glass Co Ltd
Priority to JP2006510726A priority Critical patent/JP4971789B2/ja
Priority to US10/591,066 priority patent/US20080138697A1/en
Priority to EP05719953A priority patent/EP1727225A4/fr
Priority to CA002557828A priority patent/CA2557828A1/fr
Publication of WO2005086265A1 publication Critical patent/WO2005086265A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
    • D21H13/36—Inorganic fibres or flakes
    • D21H13/38—Inorganic fibres or flakes siliceous
    • D21H13/40—Inorganic fibres or flakes siliceous vitreous, e.g. mineral wool, glass fibres
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C14/00—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix
    • C03C14/002—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix the non-glass component being in the form of fibres, filaments, yarns, felts or woven material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/54—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving
    • D04H1/542—Adhesive fibres
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/58—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
    • D04H1/64—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives the bonding agent being applied in wet state, e.g. chemical agents in dispersions or solutions
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0289—Means for holding the electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1058—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties
    • H01M8/106—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties characterised by the chemical composition of the porous support
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1058—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties
    • H01M8/1062—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties characterised by the physical properties of the porous support, e.g. its porosity or thickness
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2214/00—Nature of the non-vitreous component
    • C03C2214/02—Fibres; Filaments; Yarns; Felts; Woven material
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2214/00—Nature of the non-vitreous component
    • C03C2214/30—Methods of making the composites
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2383/02—Polysilicates
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—Inorganic compounds
    • D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
    • D21H17/68—Water-insoluble compounds, e.g. fillers, pigments siliceous, e.g. clays
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates to a proton conductive membrane reinforcing material used as an electrolyte membrane for a fuel cell.
  • the present invention also relates to a proton conductive membrane and a fuel cell using the reinforcing material.
  • Fuel cells have attracted attention as environmentally friendly energy sources because of their high power generation efficiency and low environmental load. Fuel cells are generally classified into several types depending on the type of electrolyte. Above all, polymer electrolyte fuel cells (PEFCs) are high in output, easy to reduce in size and weight, and can be expected to reduce costs through mass production. Therefore, the polymer electrolyte fuel cell is useful as a power source for small-scale on-site type, automobile, portable, and the like.
  • PEFCs polymer electrolyte fuel cells
  • a fluoropolymer membrane having perfluoroalkylene as a main skeleton and having an ion exchange group such as a sulfonic acid group or a carboxylic acid group is mainly used. ing.
  • Japanese Patent Application Laid-Open No. 2001-345111 discloses a method of mixing and dispersing a reinforcing material such as a fibril-like fluorocarbon polymer into a proton exchange membrane having a sulfonic acid group and a perfluorocarbon polymer. Have been.
  • Japanese Patent Application Laid-Open No. 2003-142122 discloses that, in order to produce a film that is not broken even when thinned by a hot press, a polymer solid is prepared by stretching expanded porous polytetrafluoroethylene. A method for impregnating an electrolyte is disclosed.
  • Japanese Patent Application Laid-Open No. 11-204121 discloses that a fluoropolymer is reinforced with an inorganic fiber surface-treated with a silane coupling agent, and a hydrocarbon polymer is graft-polymerized on the fluoropolymer. Later, a method for introducing a sulfonic acid group into the obtained polymer was disclosed! Puru.
  • Japanese Patent Application Laid-Open No. 2001-307545 discloses a composite film of an organic polymer such as polyethylene oxide and a three-dimensional crosslinked structure of a metal oxide such as silicon, titanium, and zirconium.
  • a method of reinforcing with a reinforcing material is disclosed.
  • the reinforcing material there are disclosed fibers of a polymer material such as acrylic, polyester, polypropylene, and fluororesin, fibers of a natural material such as silk, cotton, and paper, and glass fibers.
  • JP-A-2001-307545 describes that it is preferable to use glass fiber and its woven fabric in view of strength and affinity with a film composition.
  • Japanese Patent Application Laid-Open No. 10-312815 discloses a composite membrane in which an ion-conductive polymer is embedded in a randomly oriented porous support having individual fiber strength. Porous supports have been used to improve the dimensional stability and handleability of composite membranes.
  • JP-A-10-312815 exemplifies glass, polymer, ceramic, quartz, silica, carbon or metal fibers as suitable fibers, preferably glass, ceramic or quartz fibers. It is stated that there is something.
  • the fibril-like fluorocarbon polymer disclosed in JP-A-2001-345111 and the expanded porous polytetrafluoroethylene disclosed in JP-A-2003-142122 are generally commercially available porous materials, For example, it is extremely expensive compared to glass fiber nonwoven fabric and woven fabric.
  • polyolefin-based porous materials such as polypropylene nonwoven fabric and polyethylene porous film, which are known as inexpensive and high-strength porous materials, have insufficient heat resistance and acid resistance required for proton conductive membranes for fuel cells. is there.
  • the needle fiber embedded in the electrolyte membrane and the fluorine-based polymer are bonded by a silane coupling agent, and thereby the tensile strength of the electrolyte membrane is increased. Is enhanced. Therefore, it is disclosed in Japanese Patent Application Laid-Open No. 11-204121.
  • the reinforcing fibers themselves form a three-dimensional structure. In fact, the length of the inorganic fibers used in the examples of JP-A-11 204121 is as short as about 20 m (fiber diameter 0.6 m, aspect ratio 33).
  • crushed glass fibers having a length of 70 m and a fiber diameter of 10 ⁇ m are mixed in the electrolyte membrane.
  • the tensile strength is improved to some extent.
  • the effect of suppressing dimensional change due to swelling due to water content of the polymer film and shrinkage during drying and curing is not sufficient.
  • Japanese Patent Application Laid-Open No. 10-312815 discloses an example in which a commercially available glass fiber non-woven fabric, a wet-formed sheet made of a mixture of cut glass fiber and glass microfiber is used as a reinforcing material, and a sheet of quartz fiber is used as a reinforcing material. Is disclosed.
  • the inside of the proton conductive membrane of the fuel cell is in an acidic environment, and its reinforcing material is required to have high acid resistance. Therefore, general glass compositions, for example, E glass compositions, which are often used as glass fibers, are inadequate due to poor acid resistance. In the E glass composition, the alkaline component elutes from the inside of the glass fiber due to long-term use.
  • the proton conductive membrane used in the fuel cell is required to have a small dimensional change upon swelling in addition to a high tensile strength.
  • an object of the present invention is to provide a reinforcing material used for a proton conductive membrane of a fuel cell, which is excellent in heat resistance, acid resistance and dimensional stability. Further, another object of the present invention is to provide a proton conductive membrane and a fuel cell using the reinforcing material.
  • the reinforcing material of the present invention is a reinforcing material for a proton conductive membrane, and includes a nonwoven fabric having glass fiber having a C glass composition and a binder that strengthens the binding between the glass fibers as main components.
  • the average fiber diameter of the glass fibers is in the range of 0.1 ⁇ m to 20 m, and the average fiber length of the glass fibers is in the range of 0.5 mm to 20 mm.
  • the “main component” means that the sum of the content of the glass fiber having the C glass composition and the content of the binder is 90% by mass or more.
  • the proton conductive membrane of the present invention is a proton conductive membrane including a proton conductive substance and a reinforcing material, wherein the reinforcing material is the reinforcing material of the present invention.
  • the fuel cell of the present invention is a fuel cell including a proton conductive membrane, wherein the proton conductive membrane includes a proton conductive substance and a reinforcing material, and the reinforcing material is the reinforcing material of the present invention. Material.
  • the reinforcing material of the present invention has a skeleton formed by glass fibers having a C glass composition and a binder, sufficient strength can be maintained even in a high-temperature acidic environment where heat resistance and acid resistance are high. . Further, the reinforcing material of the present invention exhibits excellent dimensional stability and tensile strength because the glass fibers are bound by the binder. Further, the reinforcing material of the present invention can be manufactured at low cost.
  • a proton conductive membrane having excellent mechanical strength, dimensional stability, handleability, and durability and exhibiting good proton conductivity can be obtained. Furthermore, a fuel cell with high power generation efficiency can be obtained by configuring a fuel cell using this proton conductive membrane.
  • FIG. 1 is an electron micrograph showing an example of a reinforcing material of the present invention.
  • FIG. 2 is an electron micrograph showing another example of the reinforcing material of the present invention.
  • FIG. 3 is a cross-sectional view schematically showing a structure of a proton conductive membrane of the present invention.
  • the reinforcing material of the present invention is a reinforcing material for a proton conductive membrane.
  • the reinforcing material includes a nonwoven fabric mainly composed of glass fibers having a C glass composition and a binder for strengthening the bonding between the glass fibers.
  • the sum of the content of the glass fiber having the C glass composition and the content of the binder is 90% by mass or more (eg, 95% by mass or more), and is typically 99% by mass or more (eg, 100% by mass). ).
  • the binding between the glass fibers is strengthened by the binder.
  • the average fiber diameter of glass fibers is in the range of 0.1 ⁇ m-20 ⁇ m.
  • the average fiber length of glass fiber is 0.5mm-20mm In the range.
  • C glass fibers (glass fibers having a C glass composition) are fibers used in lead-acid batteries and the like.
  • the C glass composition has the highest acid resistance among known compositions for glass fibers.
  • Table 1 shows general C glass compositions applicable to the present invention.
  • R O represents the sum of Na O and K O. 0 ⁇ [Na O] ⁇ 19 (% by mass), 0
  • the C glass composition may contain trace components, not shown in Table 1!
  • the thickness of the nonwoven fabric (reinforcing material) serving as the skeleton of the electrolyte membrane is preferably 400 m or less, more preferably 100 m or less. / zm or less, for example 50 m or less.
  • the term “thickness of the nonwoven fabric” means a value obtained by measuring the thickness of the nonwoven fabric pressed at a pressure of 20 kPa with a dial gauge.
  • the average fiber diameter of the glass fibers constituting the nonwoven fabric needs to be in the range of 0.1 m to 20 ⁇ m, and preferably in the range of 0.3 m to 8 m. If the average fiber diameter is less than 0.1 ⁇ m, the production cost becomes extremely high. On the other hand, if the average fiber diameter exceeds 20 m, it becomes difficult to form a nonwoven fabric having a uniform thickness. In addition, a plurality of types of glass fibers having different average fiber diameters may be mixed and used. [0030] The average fiber length of the glass fibers constituting the nonwoven fabric needs to be in the range of 0.5mm to 20mm, and preferably in the range of 2mm to 15mm.
  • the average fiber length is less than 0.5 mm, the mechanical strength of the nonwoven fabric will be significantly reduced, and the effect of reinforcing the electrolyte membrane will be reduced, resulting in extremely poor handling.
  • the average fiber length exceeds 20 mm, the dispersibility of the glass fibers during the formation of the nonwoven fabric will decrease, and the uniformity of the thickness and the uniformity of the basis weight will decrease. As a result, a nonwoven fabric suitable for reinforcing the electrolyte membrane cannot be obtained.
  • the dimensional stability and tensile strength of the nonwoven fabric depend only on the entanglement of the fibers. Therefore, the bonding between the fibers is weak.
  • the glass fibers that adhere to it also move.
  • thin C glass fibers having a diameter of 20 / zm or less are difficult to elongate, and therefore the binding force between the short glass fibers is very weak. Therefore, when the nonwoven fabric is composed of only C glass fibers, the dimensional stability required for the proton conductive membrane of the fuel cell cannot be obtained.
  • the glass fibers are restrained with each other using a binder, and the dimensional stability and strength of the nonwoven fabric are increased.
  • the nodder may include an inorganic nodder. By fixing the intersection of glass fibers with an inorganic binder, a three-dimensional structure with high dimensional stability can be formed.
  • the addition amount of the inorganic binder may be in the range of 0.5% to 10% (more preferably, 2% to 9%) of the mass of the glass fiber. By setting the content within this range, a reinforcing material having excellent mechanical properties can be obtained without significantly lowering the proton conductivity.
  • the inorganic binder for example, silica (silicon oxide) can be used, but other inorganic materials may be used.
  • the binder may include an organic binder. These inorganic binder and organic binder can be formed of a liquid binder described later.
  • the binder may include a binder formed using a liquid containing a component of the binder (hereinafter, may be referred to as a "liquid binder").
  • the liquid binder is not particularly limited as long as a binder having high heat resistance and acid resistance after curing can be obtained.
  • solvents or dispersion media for example, water, various alcohols, or mixtures thereof can be used.
  • the liquid binder may contain a dispersant, a surfactant, a pH adjuster, a flocculant and the like.
  • the amount of the binder to be added (the solid content of the liquid binder) is such that the amount of the attached binder is 0.5% to 10% (more preferably 2% to 9%) of the mass of the glass fiber. It is preferable that the amount falls within the range. If the amount of the binder attached is less than 0.5% of the mass of the glass fiber, the bonding effect between the glass fibers by the binder becomes low. On the other hand, if the amount of the binder attached exceeds 10% of the mass of the glass fiber, a large number of membranes are formed between the glass fibers, and proton conduction may be inhibited.
  • the liquid binder it is particularly preferable to use colloidal silica having excellent acid resistance and heat resistance.
  • the binder may include a fibrous binder!
  • the caloric content of the fibrous binder is preferably in the range of 1% to 40% (more preferably, 2% to 30%) of the mass of the glass fiber.
  • the addition amount is less than 1% of the mass of the glass fiber, the effect of the binder for bonding or entanglement between the glass fibers is reduced.
  • the added amount exceeds 40% of the mass of the glass fiber, the dispersion of the glass fiber becomes insufficient or a film is formed between the glass fibers. As a result, it may be difficult to make the proton conductive polymer sufficiently penetrate between the glass fibers.
  • the fibrous binder a fibrous substance that generates a physical and / or Z-binding force between glass fibers and / or between fibrous binders is used. Further, the fibrous binder is preferably made of a material having high heat resistance and acid resistance. Examples of such a fibrous binder include beaten cellulose, acrylic fiber, fluororesin fiber, aramide fiber, polyester fiber, and polyolefin fiber. Among these, beaten cellulose and polyester fiber have the advantage of having high heat resistance and adhesiveness.
  • the diameter of the fibrous binder is preferably 20 m or less. However, in the case where the fibrous binder is deformed or melted during the manufacturing process of the nonwoven fabric and no projection is formed on the nonwoven fabric, the diameter may exceed 20 m.
  • the preferred length of the fibrous binder varies depending on the material, diameter, shape, and hydrophilicity of the fibrous binder.
  • An example length of the fibrous binder may be in the range of 0.2mm-20mm.
  • inorganic binder organic binder, liquid binder, and fibrous binder may be used alone or in combination of two or more.
  • the nonwoven fabric of the present invention used as a reinforcing material preferably has a uniform basis weight and a uniform thickness.
  • the basis weight (mass per unit area) of the nonwoven fabric is preferably in the range of 2 to 50 g / m 2 , and more preferably 3 to 25 g / m 2. More preferably, it is in the range of 2 .
  • the basis weight is less than 2 gZm 2 , the entanglement between the short glass fibers is reduced, and the tensile strength is reduced.
  • the basis weight exceeds 50GZm 2, too thick as reinforcement material for the electrolyte membrane, if a high density by press or the like in order to thin it becomes shorter broken glass fibers at the mating point, The tensile strength may be significantly reduced
  • the porosity of the nonwoven fabric is preferably in the range of 60 to 98% by volume. If the porosity exceeds 98% by volume, the strength decreases. In addition, the rigidity is reduced, and the role of suppressing deformation due to contraction of the electrolyte is also reduced. On the other hand, if the porosity is less than 60% by volume, the proton conductivity of the electrolyte membrane decreases. The porosity is more preferably in the range of 80-98% by volume, and even more preferably in the range of 90-95% by volume.
  • An example of wet-making glass staple fibers with an average diameter of about 0.1 ⁇ ⁇ ⁇ ⁇ and an average length of about 4 mm without a mechanical compression process is a nonwoven fabric with a thickness of 30 m and a porosity of about 95% by volume. It can be made.
  • the value of the porosity V (vol%), the non-woven fabric having a thickness of t (m), the mass W per unit area of the nonwoven fabric (kg / m 2), the density of the glass fibers p G (about 2. 5 X 10 3 kg / m 3 ), the true density p B of the binder material (kgZm 3), using a mass ratio cB of the binder to the glass fibers, is determined from the following [equation 1].
  • the thickness t of the nonwoven fabric is the thickness of the nonwoven fabric pressurized at a pressure of 20 kPa. The thickness is a value measured with a dial gauge.
  • the true density pB is a density that does not include voids, and is a density when only the volume occupied by the substance itself is used as a volume for density calculation.
  • V (%) [1—WZt X ⁇ (l—cB) Z / oG + cBZ / oB ⁇ ] X100
  • the reinforcing material according to the present invention may be subjected to a surface treatment.
  • the surface of the nonwoven fabric may be treated with a silane coupling agent.
  • the glass fiber may be subjected to a surface treatment such as forming a coating such as silica.
  • the surface treatment method is not particularly limited as long as it does not impair the heat resistance and acid resistance of the glass fiber.
  • a surface treatment of the glass fiber with a silane coupling agent is effective.
  • the adhesion between the glass fiber and the proton conductive polymer is improved, and the above-mentioned formation of minute peeling is suppressed.
  • the reinforcing effect of the glass fiber becomes extremely high.
  • deposition amount of the silane coupling agent is preferably in the range of surface area lm 2 per 0. 5mg- 200m g of glass fibers. If the amount is less than 0.5 mg / m 2 , the silane coupling agent cannot sufficiently cover the glass fiber surface, and the effect of improving the adhesive strength between the glass fiber and the polymer will be reduced.
  • the adhesive strength of the adhesion amount is more than 200MgZm 2, formed with a layer of force becomes low intensity only silane between the glass fibers and the polymer tends to occur destruction in that layer, the glass fiber and polymer The improvement effect decreases.
  • the silane coupling agent used in the reinforcing material of the present invention is not particularly limited as long as it exhibits an effect of improving the adhesive strength between the glass fiber and the proton conductive polymer, but is easy to handle. Therefore, aminosilane or acrylic silane is preferred! /. [0053] Since the above-described silane coupling agent treatment and the above-described binder addition exhibit a reinforcing effect by independent mechanisms, they can be used in combination, and the effects are synergistic. .
  • the reinforcing material of the present invention can be produced, for example, by the following two methods.
  • a mixed solution containing glass fibers having a C glass composition and a binder component for strengthening the binding between the glass fibers is prepared (step (i)).
  • the glass fiber the above-described glass fiber is used.
  • the components of the binder the liquid binder and the fibrous binder described above are used.
  • the mixed solution in step (i) may contain a dispersant, a surfactant, a pH adjuster, a flocculant and the like.
  • a nonwoven fabric containing a glass fiber and a binder is formed from the mixed solution (step (ii)).
  • the nonwoven fabric can be formed by, for example, a general wet papermaking method. After forming the nonwoven fabric, heat treatment or the like may be performed as necessary.
  • a nonwoven fabric in which the glass fibers are restrained by the nodder is obtained.
  • FIG. 1 shows an electron micrograph of an example of the reinforcing material formed by the first method using the mixed solution containing colloidal silica.
  • the silica particles are attached not only to the intersections of the glass fibers but also to the surfaces of the glass fibers, and irregularities are formed on the surface of the glass fibers, which also have a silica force.
  • a nonwoven fabric is formed from glass fibers having a C glass composition (step
  • the nonwoven fabric can be formed by, for example, a general wet papermaking method.
  • a liquid containing a binder component is applied to the nonwoven fabric, and then dried, thereby strengthening the binding between the glass fibers with the binder (step (()).
  • the liquid binder described above is used as the liquid containing the components of the binder. If necessary, heat treatment may be performed after drying.
  • the application of the liquid binder may be performed by immersing the nonwoven fabric in the liquid binder, or may be performed by impregnating the nonwoven fabric with the liquid binder.
  • FIG. 2 shows an electron micrograph of an example of the reinforcing material formed by the second method using colloidal silica as a liquid binder.
  • silica mainly adheres to intersections of glass fibers and forms a film at the intersections.
  • the first method has an advantage that the manufacturing process is simple.
  • the second method it is possible to concentrate the binder at the intersection of the glass fibers, and if the effect is obtained with a small amount of the binder, a high V!
  • the treatment may be performed after the above-described steps.
  • the treatment with the silane coupling agent can be performed by a general method using a general silane coupling agent.
  • the proton conductive membrane of the present invention includes a proton conductive substance and the reinforcing material of the present invention.
  • Known substances that are not particularly limited as the proton conductive substance can be used.
  • a polymer electrolyte such as a fluorine-based polymer electrolyte, a hydrocarbon-based polymer electrolyte, or a chemically modified fullerene-based proton conductor may be used.
  • an inorganic proton conductor or an inorganic-organic composite proton conductor may be used.
  • a silicate solid electrolyte such as a phosphosilicate solid electrolyte may be used.
  • a proton conductive polymer having perfluoroalkylene as a main skeleton and having an ion exchange group such as a sulfonic acid group or a sulfonic acid group may be used.
  • Nafion (registered trademark) membrane manufactured by Du Pont
  • Dow membrane manufactured by Dow Chemical
  • Aciplex registered trademark
  • Flemion registered trademark
  • the proton conductive membrane can be formed, for example, by impregnating the nonwoven fabric of the present invention with a liquid in which a proton conductive substance such as a proton conductive polymer is dispersed or dissolved, and then drying. After drying, heat treatment may be performed.
  • the proportion of the reinforcing material of the present invention in the proton conductive membrane is preferably in the range of 115 to 50% by mass.
  • the fuel cell of the present invention is a fuel cell including a proton conductive membrane, and the proton transfer
  • the conductive membrane contains a proton conductive substance and the reinforcing material of the present invention. That is, the proton conductive membrane is the above-described proton conductive membrane of the present invention. Parts other than the proton conductive membrane are not particularly limited, and the same configuration as a known fuel cell can be applied, for example, the same configuration as a polymer electrolyte fuel cell can be applied. For example, a known fuel electrode and a known air electrode are arranged on both sides of the proton conductive membrane of the present invention.
  • Glass short fibers having the C glass composition shown in Table 2 and having an average diameter of 0.7 m and an average length of about 3 mm were prepared. 95 parts by mass of this glass fiber and 5 parts by mass of beaten cellulose fiber are simultaneously put into a pulper for loosening the fiber, and sufficiently dissociated and dispersed in an aqueous solution adjusted to pH 2.5 with sulfuric acid. A slurry for papermaking was prepared.
  • R O represents the sum of Na O and K O, and Na O is about 612% by mass.
  • K O is about 06% by mass.
  • a glass fiber nonwoven fabric having a thickness of m and a basis weight of 8 gZm 2 was prepared from the slurry.
  • the obtained nonwoven fabric contained the above-mentioned two types of fibers at the above-mentioned compounding ratio.
  • the porosity of this nonwoven fabric was about 95% by volume.
  • this reinforcing material is impregnated with a dispersion of a fluoropolymer electrolyte, and is After air drying, heat treatment was performed at 120 ° C for 1 hour. Thus, a proton conductive membrane was produced.
  • the electrolyte dispersion was prepared by diluting Nafion DE2020 (manufactured by DuPont) with isopropyl alcohol. The concentration and impregnation amount of the electrolyte dispersion were adjusted so that the thickness of the electrolyte membrane after the heat treatment became 50 m. Thus, a proton conductive membrane was obtained.
  • FIG. 3 schematically shows the structure of this proton conductive membrane.
  • the proton conductive membrane 1 is composed of a reinforcing material (nonwoven fabric) 10 and a fluoropolymer electrolyte 20 impregnated in the reinforcing material 10.
  • the glass fiber content in the proton conductive membrane was calculated to be about 12% by mass from the densities of the glass fibers and the electrolyte, and the porosity of the nonwoven fabric.
  • the nonwoven fabric prepared in Example 1 was impregnated with a silane coupling agent, and then heat-treated at 120 ° C. for 1 hour in an oven.
  • a reinforcing material of the present invention containing a fibrous binder and having a surface treated with a silane coupling agent was obtained.
  • the silane coupling agent an aqueous solution obtained by dissolving aminosilane in ion-exchanged water was used.
  • solid content adhesion quantity of surface area lm 2 per glass fibers was adjusted to be 10 mg.
  • This reinforcing material was impregnated with an electrolyte dispersion in the same procedure as in Example 1 to obtain a proton conductive membrane.
  • the nonwoven fabric After impregnating the nonwoven fabric prepared in Example 1 with a liquid binder, the nonwoven fabric was dried in an oven at 100 ° C. for 30 minutes. Thus, the reinforcing material of the present invention containing the inorganic binder (silica) and the fibrous binder was obtained.
  • the liquid binder was prepared by diluting colloidal silica (manufactured by Nissan Chemical Industries, Ltd., trade name: Snowtex O) with pure water. At this time, the concentration of the colloidal silica diluent and the amount of impregnation were adjusted so that the amount of silica attached to the glass fibers was 5% by mass.
  • This reinforcing material was impregnated with the electrolyte dispersion in the same procedure as in Example 1 to obtain a proton conductive membrane.
  • the nonwoven fabric prepared in Example 3 was impregnated with a silane coupling agent, and then heat-treated at 120 ° C. for 1 hour in an oven. In this way, including the inorganic binder and the fibrous binder, A reinforcing material of the present invention whose surface was treated with a silane coupling agent was obtained.
  • a silane coupling agent an aqueous solution obtained by dissolving aminosilane in ion-exchanged water was used. At this time, the concentration and the impregnation amount of the aminosilane aqueous solution were adjusted so that the solid adhesion amount per lm 2 of the glass fiber became 10 mg.
  • This reinforcing material was impregnated with the electrolyte dispersion in the same procedure as in Example 1 to obtain a proton conductive membrane.
  • Example 1 Using only the glass fibers used in Example 1, a nonwoven fabric made of only glass fibers was formed by the same papermaking process as in Example 1. This nonwoven fabric was subjected to a colloidal silica treatment in the same manner as in Example 3. Thus, a reinforcing material of the present invention containing silica was obtained. This reinforcing material was impregnated with the electrolyte dispersion in the same procedure as in Example 1 to obtain a proton conductive membrane.
  • the electrolyte dispersion used in Example 1 was placed in a glass plate having a bottom surface with good flatness, air-dried for 12 hours or more, and then heat-treated at 120 ° C. for 1 hour. Thus, a proton conductive membrane containing no reinforcing material was obtained.
  • the concentration of the electrolyte dispersion was the same as in Example 1, and the amount of the liquid was adjusted so that the thickness of the electrolyte membrane after the heat treatment became 50 m.
  • the nonwoven fabric produced in Example 1 was pulverized by applying a pressure of about lOMPa to obtain a fine glass fiber powder.
  • This fine powder is impregnated with a silane coupling agent, and then heat-treated in an oven at 120 ° C for 1 hour to obtain a glass fiber fine powder whose surface has been treated with the silane coupling agent (average fiber length less than 0.5 mm). )
  • the silane coupling agent an aqueous solution obtained by dissolving aminosilane in ion-exchanged water was used. At this time, the concentration and the impregnation amount of the aminosilane aqueous solution were adjusted so that the solid adhesion amount per lm 2 of the surface area of the glass fiber became 10 mg.
  • This glass fiber fine powder was mixed with the same electrolyte dispersion as in Example 1 so that the ratio of the glass fiber fine powder to the electrolyte was about 12% by mass. Then, the mixed solution was stirred for 5 minutes at a rotation speed of 1.67 rotations Z seconds (100 rpm) using a paint shaker. Thus, an electrolyte dispersion containing the glass fiber fine powder was obtained. This is called flatness It was placed in a glass Petri dish having a good bottom surface, air-dried for 12 hours or more, and then heat-treated at 120 ° C for 1 hour to obtain a proton conductive membrane. The concentration of the electrolyte dispersion was the same as in Example 1, and the amount of the liquid was adjusted so that the thickness of the proton conductive membrane after the heat treatment became 50 m.
  • the proton conductive membrane was cut to prepare a test piece having a width of 20 mm and a length of 80 mm.
  • the test piece was gripped by two chucks with a chuck interval of 30 mm, and pulled at a speed of 10 mmZ to measure the load (N) at break. This was divided by the measured values of the sample thickness and width to calculate the tensile strength (MPa). Sample thickness was measured with a micrometer
  • the proton conductive membrane was cut to prepare a test piece of about 40 mm X about 70 mm, and the dimensions (length and width) in a dry state were measured.
  • the test piece was immersed in ion-exchanged water for 12 hours or more, and the dimensions (length and width) in a hydrated state were measured again. From the measurement results, the area of the test piece in a dry state and the area of the test piece in a hydrated state were calculated, and these were substituted into the following [Equation 2] to calculate the area swelling ratio.
  • the area swelling rate is an area increasing rate due to swelling of the proton conductive membrane due to water content.
  • the proton conductive membrane was placed in a wet state, and the proton conductivity was measured by a direct current two-terminal method using an impedance analyzer.
  • the electrolyte membranes of Examples 15 of the present invention have higher tensile strengths than the electrolyte membranes of Comparative Examples 1 and 2.
  • the area swelling ratios of Examples 1 to 5 were greatly reduced as compared with Comparative Examples.
  • the effect of suppressing dimensional changes in Examples 2-5 using a liquid binder (inorganic binder) was remarkable.
  • Comparative Example 2 The tensile strength and swelling ratio of Comparative Example 2 containing about 12% by mass of the glass fiber fine powder subjected to the aminosilane treatment were significantly different from the results of Comparative Example 1 containing no glass fiber. In comparison, Comparative Example 2 was significantly inferior in tensile strength and swelling ratio as compared with Example 2 containing about 12% by mass of a glass fiber nonwoven fabric similarly treated with aminosilane. From the above, it was shown that the fiber length was extremely short and the reinforcing effect was low with a proton conductive membrane using glass fiber fine powder.
  • Glass fibers having an average fiber diameter of about 0.4 m (C glass composition) and glass fibers having an average fiber diameter of about 0 (C glass composition) were collected at a mass ratio of 4: 1. Both the glass fibers and colloidal silica, and poured into water adjusted to P H2.5 with sulfuric acid to obtain their mixture. The added amount of colloidal silica was about 40% of the total mass of the two types of glass fibers. Next, the mixed solution was put into a pulper and stirred at 50 revolutions / second (3000 rpm) for about 10 minutes to obtain a slurry.
  • This slurry was diluted with water adjusted to pH 2.5 with sulfuric acid, and further stirred, It passed through a net with an aperture of 0.5 mm or less. Then, the glass fiber remaining on the net was dried to obtain a reinforcing material (thickness: 50 m) of the present invention having a glass fiber strength containing silica.
  • the proportion of the binder (silica) in the reinforcing material was about 29% by mass.
  • Example 1 The tensile strength of each of the reinforcing materials (nonwoven fabric) of Example 6 and Comparative Example 3 was measured. As a result, the tensile strength of the reinforcing material of Example 1 was about 2.2 MPa. The tensile strength of the reinforcing material of Example 6 was about 1.9 MPa. The tensile strength of the reinforcing material of Comparative Example 3 was about 0.4 MPa.
  • the reinforcing material of the present invention can be applied to reinforcement of a proton conductive membrane of a fuel cell.
  • the proton conductive membrane using this reinforcing material can be applied to a fuel cell.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Textile Engineering (AREA)
  • Ceramic Engineering (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Fuel Cell (AREA)
  • Reinforced Plastic Materials (AREA)
  • Conductive Materials (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Nonwoven Fabrics (AREA)

Abstract

Il est prévu un matériau de renfort pour membranes conductrices protoniques contenant un tissu non tissé composé essentiellement de fibres de verre de la composition de verre C et un liant pour renforcer la liaison entre ces fibres. Les fibres de verre ont un diamètre de fibre moyen de 0,1-20 µm, et une longueur de fibre moyenne de 0,5-20 mm. Ce matériau de renfort est excellent en matière de résistance thermique, de résistance aux acides et de stabilité des cotes.
PCT/JP2005/003649 2004-03-04 2005-03-03 Matériau de renfort pour membrane conductrice protonique, membrane conductrice protonique utilisant ledit matériau et une cellule électrochimique Ceased WO2005086265A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP2006510726A JP4971789B2 (ja) 2004-03-04 2005-03-03 プロトン伝導性膜用補強材およびそれを用いたプロトン伝導性膜および燃料電池
US10/591,066 US20080138697A1 (en) 2004-03-04 2005-03-03 Reinforcing Material For Proton Conductive Membrane, and Proton Conductive Membrane Using the Same and Fuel Cell
EP05719953A EP1727225A4 (fr) 2004-03-04 2005-03-03 Maté riau de renfort pour membrane conductrice protonique, membrane conductrice protonique utilisant ledit maté riau et une cellule électrochimique
CA002557828A CA2557828A1 (fr) 2004-03-04 2005-03-03 Materiau de renfort pour membrane conductrice protonique, membrane conductrice protonique utilisant ledit materiau et une cellule electrochimique

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2004-060808 2004-03-04
JP2004060808 2004-03-04
JP2004102787 2004-03-31
JP2004-102787 2004-03-31

Publications (1)

Publication Number Publication Date
WO2005086265A1 true WO2005086265A1 (fr) 2005-09-15

Family

ID=34921682

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2005/003649 Ceased WO2005086265A1 (fr) 2004-03-04 2005-03-03 Matériau de renfort pour membrane conductrice protonique, membrane conductrice protonique utilisant ledit matériau et une cellule électrochimique

Country Status (6)

Country Link
US (1) US20080138697A1 (fr)
EP (1) EP1727225A4 (fr)
JP (2) JP4971789B2 (fr)
KR (1) KR100821027B1 (fr)
CA (1) CA2557828A1 (fr)
WO (1) WO2005086265A1 (fr)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007194133A (ja) * 2006-01-20 2007-08-02 Toshiba Corp 電解質膜、膜電極複合体及び燃料電池
JP2010015835A (ja) * 2008-07-03 2010-01-21 Japan Vilene Co Ltd ガス拡散層、膜−電極接合体及び燃料電池
JP2010185164A (ja) * 2009-01-14 2010-08-26 Japan Vilene Co Ltd 無機系繊維不織布及びその製造方法
WO2011111367A1 (fr) 2010-03-08 2011-09-15 日本板硝子株式会社 Feuille de renforcement pour membrane d'électrolyte solide
KR20110119684A (ko) * 2009-01-14 2011-11-02 니혼바이린 가부시기가이샤 무기계 섬유 구조체 및 그 제조 방법
JP2012114050A (ja) * 2010-11-26 2012-06-14 Nippon Sheet Glass Co Ltd 固体電解質膜補強材
US8257825B2 (en) * 2005-01-12 2012-09-04 Samsung Sdi Co., Ltd. Polymer electrode membrane for fuel, and membrane-electrode assembly and fuel cell system comprising the same
JP2012529144A (ja) * 2009-06-04 2012-11-15 コリア リサーチ インスティチュート オブ ケミカル テクノロジー セラミック多孔性支持体、それを用いた強化複合電解質膜及びそれを備えた膜−電極アセンブリー
JP2012252915A (ja) * 2011-06-03 2012-12-20 Kaneka Corp 高分子電解質膜、およびその利用
JP2013152938A (ja) * 2006-08-02 2013-08-08 Basf Fuel Cell Gmbh 性能の改善された膜電極接合体および燃料電池
WO2015001707A1 (fr) * 2013-07-01 2015-01-08 日本板硝子株式会社 Matériau de renfort pour film conducteur de protons, film conducteur de protons comprenant ledit matériau, et pile à combustible polymère solide
JP2016139587A (ja) * 2015-01-29 2016-08-04 国立大学法人山梨大学 高分子電解質膜、膜／電極接合体および燃料電池

Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005086265A1 (fr) * 2004-03-04 2005-09-15 Nippon Sheet Glass Company, Limited Matériau de renfort pour membrane conductrice protonique, membrane conductrice protonique utilisant ledit matériau et une cellule électrochimique
JP2008204945A (ja) * 2007-01-23 2008-09-04 Japan Vilene Co Ltd ガス拡散電極用基材、ガス拡散電極及びその製造方法、並びに燃料電池
JP5320522B2 (ja) * 2011-08-09 2013-10-23 パナソニック株式会社 固体高分子型燃料電池用電解質膜およびその製造方法、並びに、固体高分子型燃料電池
PL2768046T3 (pl) * 2011-10-11 2021-08-30 Exide Technologies, S.L.U. Zalewany akumulator kwasowo-ołowiowy z elektrodami zawierającymi podłoże aplikacyjne
JP5752584B2 (ja) * 2011-12-16 2015-07-22 日本板硝子株式会社 セパレータ
US20130330653A1 (en) * 2012-06-08 2013-12-12 GM Global Technology Operations LLC Novel PPS-S Membrane
US20140045094A1 (en) * 2012-08-07 2014-02-13 GM Global Technology Operations LLC PPS Membrane Reinforcing Material
EP2888772B1 (fr) * 2012-08-22 2020-06-03 Daramic, LLC Séparateur de batterie à tissu non tissé imprégné de gel pour batterie au plomb-acide
CN103633367B (zh) * 2012-08-28 2016-12-21 比亚迪股份有限公司 一种凝胶聚合物电解质和聚合物锂离子电池及其制备方法
MY199418A (en) 2014-06-17 2023-10-26 Ocv Intellectual Capital Llc Water loss reducing pasting mats for lead-acid batteries
US11380962B2 (en) * 2014-06-17 2022-07-05 Owens Corning Intellectual Capital, Llc Anti-sulphation pasting mats for lead-acid batteries
US9972863B2 (en) 2016-07-29 2018-05-15 Blue Current, Inc. Compliant solid-state ionically conductive composite electrolytes and materials
US10079404B1 (en) 2017-03-03 2018-09-18 Blue Current, Inc. Polymerized in-situ hybrid solid ion-conductive compositions
JP6879844B2 (ja) * 2017-06-30 2021-06-02 帝人株式会社 釣り具用部材及びそれを用いた釣り用リールのドラグ装置
US11581570B2 (en) * 2019-01-07 2023-02-14 Blue Current, Inc. Polyurethane hybrid solid ion-conductive compositions
WO2021127542A1 (fr) 2019-12-20 2021-06-24 Blue Current, Inc. Électrolytes composites avec liants
US12166239B2 (en) 2019-12-20 2024-12-10 Blue Current, Inc. Polymer microspheres as binders for composite electrolytes
US11394054B2 (en) 2019-12-20 2022-07-19 Blue Current, Inc. Polymer microspheres as binders for composite electrolytes

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0875524A2 (fr) * 1997-04-25 1998-11-04 Johnson Matthey Public Limited Company Membranes composites
JPH11204121A (ja) * 1998-01-19 1999-07-30 Aisin Seiki Co Ltd 固体高分子電解質型燃料電池
WO2000024075A1 (fr) * 1998-10-16 2000-04-27 Johnson Matthey Public Limited Company Liant pour substrat
WO2003041091A1 (fr) * 2001-10-30 2003-05-15 Sekisui Chemical Co., Ltd. Membrane conductrice de protons, son procede de production et piles a combustible obtenues au moyen de cette membrane
JP2004047450A (ja) * 2002-05-20 2004-02-12 Nippon Sheet Glass Co Ltd プロトン伝導性膜用補強材およびそれを用いたプロトン伝導性膜、ならびにそれを用いた燃料電池
JP2004319421A (ja) * 2003-02-27 2004-11-11 Nippon Sheet Glass Co Ltd プロトン伝導性膜用補強材、プロトン伝導性膜およびそれを用いた燃料電池

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0798867B2 (ja) * 1987-08-26 1995-10-25 株式会社クラレ 成形物およびその製造方法
JPH11100767A (ja) * 1997-09-29 1999-04-13 Shin Kobe Electric Mach Co Ltd 積層板用基材及びその製造法ならびにプリプレグ及び積層板
GB9914499D0 (en) * 1999-06-22 1999-08-25 Johnson Matthey Plc Non-woven fibre webs
JP4539896B2 (ja) * 1999-09-17 2010-09-08 独立行政法人産業技術総合研究所 プロトン伝導性膜、その製造方法及びそれを用いた燃料電池
CN101127401A (zh) * 2000-10-19 2008-02-20 佳能株式会社 含有磷酸基的固体高分子电解质(复合)膜及其制造方法
US7097939B2 (en) * 2001-07-13 2006-08-29 Hollingsworth & Vose Company Gel-forming battery separator
JP2003100316A (ja) * 2001-09-21 2003-04-04 Sekisui Chem Co Ltd プロトン伝導性膜およびその製造方法
JP2003166162A (ja) * 2001-11-27 2003-06-13 Matsushita Electric Works Ltd ガラス不織布及び積層板
JP2004014232A (ja) * 2002-06-05 2004-01-15 Uni-Chemical Co Ltd リン酸基及び／又はスルホン酸基を含有する固体高分子電解質（複合）膜並びにそれを用いた燃料電池
JP2004206915A (ja) * 2002-12-24 2004-07-22 Nippon Sheet Glass Co Ltd 固体高分子電解質型燃料電池セルおよびそれを用いた燃料電池
WO2005086265A1 (fr) * 2004-03-04 2005-09-15 Nippon Sheet Glass Company, Limited Matériau de renfort pour membrane conductrice protonique, membrane conductrice protonique utilisant ledit matériau et une cellule électrochimique

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0875524A2 (fr) * 1997-04-25 1998-11-04 Johnson Matthey Public Limited Company Membranes composites
JPH11204121A (ja) * 1998-01-19 1999-07-30 Aisin Seiki Co Ltd 固体高分子電解質型燃料電池
WO2000024075A1 (fr) * 1998-10-16 2000-04-27 Johnson Matthey Public Limited Company Liant pour substrat
WO2003041091A1 (fr) * 2001-10-30 2003-05-15 Sekisui Chemical Co., Ltd. Membrane conductrice de protons, son procede de production et piles a combustible obtenues au moyen de cette membrane
JP2004047450A (ja) * 2002-05-20 2004-02-12 Nippon Sheet Glass Co Ltd プロトン伝導性膜用補強材およびそれを用いたプロトン伝導性膜、ならびにそれを用いた燃料電池
JP2004319421A (ja) * 2003-02-27 2004-11-11 Nippon Sheet Glass Co Ltd プロトン伝導性膜用補強材、プロトン伝導性膜およびそれを用いた燃料電池

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8257825B2 (en) * 2005-01-12 2012-09-04 Samsung Sdi Co., Ltd. Polymer electrode membrane for fuel, and membrane-electrode assembly and fuel cell system comprising the same
JP2007194133A (ja) * 2006-01-20 2007-08-02 Toshiba Corp 電解質膜、膜電極複合体及び燃料電池
JP2013152938A (ja) * 2006-08-02 2013-08-08 Basf Fuel Cell Gmbh 性能の改善された膜電極接合体および燃料電池
JP2010015835A (ja) * 2008-07-03 2010-01-21 Japan Vilene Co Ltd ガス拡散層、膜−電極接合体及び燃料電池
KR20110119684A (ko) * 2009-01-14 2011-11-02 니혼바이린 가부시기가이샤 무기계 섬유 구조체 및 그 제조 방법
JP2010185164A (ja) * 2009-01-14 2010-08-26 Japan Vilene Co Ltd 無機系繊維不織布及びその製造方法
JP5424354B2 (ja) * 2009-01-14 2014-02-26 日本バイリーン株式会社 無機系繊維構造体及びその製造方法
US9023743B2 (en) 2009-01-14 2015-05-05 Japan Vilene Company, Ltd. Inorganic fiber structure and process for producing same
KR101681972B1 (ko) * 2009-01-14 2016-12-02 니혼바이린 가부시기가이샤 무기계 섬유 구조체 및 그 제조 방법
JP2012529144A (ja) * 2009-06-04 2012-11-15 コリア リサーチ インスティチュート オブ ケミカル テクノロジー セラミック多孔性支持体、それを用いた強化複合電解質膜及びそれを備えた膜−電極アセンブリー
WO2011111367A1 (fr) 2010-03-08 2011-09-15 日本板硝子株式会社 Feuille de renforcement pour membrane d'électrolyte solide
JP2012114050A (ja) * 2010-11-26 2012-06-14 Nippon Sheet Glass Co Ltd 固体電解質膜補強材
JP2012252915A (ja) * 2011-06-03 2012-12-20 Kaneka Corp 高分子電解質膜、およびその利用
WO2015001707A1 (fr) * 2013-07-01 2015-01-08 日本板硝子株式会社 Matériau de renfort pour film conducteur de protons, film conducteur de protons comprenant ledit matériau, et pile à combustible polymère solide
JP2016139587A (ja) * 2015-01-29 2016-08-04 国立大学法人山梨大学 高分子電解質膜、膜／電極接合体および燃料電池

Also Published As

Publication number Publication date
JPWO2005086265A1 (ja) 2008-01-24
JP4971789B2 (ja) 2012-07-11
KR20060129072A (ko) 2006-12-14
JP5226108B2 (ja) 2013-07-03
JP2011236429A (ja) 2011-11-24
EP1727225A4 (fr) 2007-10-31
KR100821027B1 (ko) 2008-04-08
EP1727225A1 (fr) 2006-11-29
CA2557828A1 (fr) 2005-09-15
US20080138697A1 (en) 2008-06-12

Similar Documents

Publication Publication Date Title
JP5226108B2 (ja) プロトン伝導性膜用補強材およびそれを用いたプロトン伝導性膜および燃料電池
KR102428982B1 (ko) 탄소 폼, 막 전극 복합체
JP4615097B2 (ja) 不織ファイバーウェブ
JP2005506406A (ja) その場重合によって調製された燃料電池用固体ポリマー膜
Yao et al. Superacidic electrospun fiber‐nafion hybrid proton exchange membranes
EP3411137A2 (fr) Membranes sélectives en céramique
JP2004079505A (ja) 燃料電池用の複合電解質
JP2012529144A (ja) セラミック多孔性支持体、それを用いた強化複合電解質膜及びそれを備えた膜−電極アセンブリー
KR20010080532A (ko) 다공질, 도전성시트 및 그 제조방법
KR20190131690A (ko) Pemfc용 복합 전해질막, 이의 제조방법 및 이를 포함하는 pemfc용 막-전극 접합체
JP6448492B2 (ja) マイクロポーラス層形成用ペースト及び燃料電池用ガス拡散層
EP3609008A1 (fr) Membrane électrolytique polymère composite
JPH09157052A (ja) 多孔質炭素板とその製造方法
EP1513212A2 (fr) Membrane à électrolyte polymère solide et pile à combustible
KR20190131689A (ko) Pemfc용 복합 전해질막, 이의 제조방법 및 이를 포함하는 pemfc용 막-전극 접합체
JP2002358981A (ja) 燃料電池用集電体及びその製造方法
KR20190131687A (ko) Pemfc용 복합 전해질막, 이의 제조방법 및 이를 포함하는 pemfc용 막-전극 접합체
JP2004363018A (ja) 固体高分子型燃料電池用多孔質電極基材
JP2004047450A (ja) プロトン伝導性膜用補強材およびそれを用いたプロトン伝導性膜、ならびにそれを用いた燃料電池
WO2016208486A1 (fr) Élément de renforcement d'électrolyte solide et film d'électrolyte solide comprenant un élément de renforcement
JP2001196085A (ja) 多孔質導電シート
JP2004319421A (ja) プロトン伝導性膜用補強材、プロトン伝導性膜およびそれを用いた燃料電池
JP2023553351A (ja) 自立型イオン選択複合膜
JP2005285549A (ja) 固体高分子型燃料電池用の電解質膜
JP5164569B2 (ja) プロトン伝導性膜用補強材およびそれを用いたプロトン伝導性膜、並びに燃料電池

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SM SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LT LU MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 2557828

Country of ref document: CA

Ref document number: 2006510726

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE

WWW Wipo information: withdrawn in national office

Country of ref document: DE

WWE Wipo information: entry into national phase

Ref document number: 2005719953

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 1020067020130

Country of ref document: KR

WWP Wipo information: published in national office

Ref document number: 2005719953

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 1020067020130

Country of ref document: KR

WWE Wipo information: entry into national phase

Ref document number: 10591066

Country of ref document: US